CN101830811B - Preparation method of 4-aminodiphenylamine - Google Patents
Preparation method of 4-aminodiphenylamine Download PDFInfo
- Publication number
- CN101830811B CN101830811B CN 201010112231 CN201010112231A CN101830811B CN 101830811 B CN101830811 B CN 101830811B CN 201010112231 CN201010112231 CN 201010112231 CN 201010112231 A CN201010112231 A CN 201010112231A CN 101830811 B CN101830811 B CN 101830811B
- Authority
- CN
- China
- Prior art keywords
- hydroxide
- ethyl
- reaction
- mol ratio
- quaternary ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 4-aminodiphenylamine, wherein a self-made mixture of bis-quaternary ammonium base and tetramethylammonium hydroxide with low price and good heat stability is used as a base catalyst for a condensation reaction of nitrobenzene and aniline. The bis-quaternary ammonium base has the structure of a general formula (I), wherein R1 and R2 are mutually independent alkyls of C1-C18 and preferentially of methyl, ethyl, n-propyl, isopropyl, allyl, butyl or dodecyl; R3, R4, R5 and R6 are mutually independent straight chain or branch chain alkyls of C1-C6 and preferentially of methyl, ethyl or propyl; and R7 is an alkylene or alkoxy substituted alkylene of C2-C6 and preferentially of ethylidene, propylidene, 2-methoxypropylidene, 2-ethyoxylpropylidene or butylidene. The preparation method has the advantages that the selectivity of the nitrobenzene in the condensation reaction and the yield of the 4-aminodiphenylamine are high; the hydrogenation speed of a base-containing condensation liquid is high; a hydrogenation liquid has high layering speed and no emulsification phenomenon; and the base has good stability and is not easy to disintegrate, thereby the recovery rate of the base catalyst is improved and the production cost is reduced.
Description
Technical field
The present invention relates to a kind of method for preparing 4-ADPA, particularly with the two quaternary ammonium hydroxides of a kind of novel self-control with make the method that oil of mirbane aniline condensation catalysts prepares 4-ADPA after Tetramethylammonium hydroxide is mixed.
Background technology
4-ADPA (4-aminodiphenylamine) has another name called 4-aminodiphenylamine, mainly for the production of p-phenylenediamine rubber aging inhibitor 4010NA, 4020 etc.
The production method of 4-ADPA has more than ten to plant, at present industrialized aniline process, formylaniline method, pentanoic method and the nitrobenzene method of mainly containing.This several method all will synthesize first 4 nitrodiphenyl amine or 4-nitrosodiphenylamine, and then reduction obtains 4-ADPA.
Nitrobenzene method is produced 4-ADPA, i.e. oil of mirbane and aniline condensation in the presence of alkaline catalysts generates 4 nitrodiphenyl amine and 4-nitrosodiphenylamine, and then hydrogenating reduction obtains 4-ADPA in the presence of catalyzer.US5117063A, US5453541A, US5451702A referring to Meng Shandou (Monsanto) company, US7504539A, US7183439B2, US6583320B2, US6395933B1, US5977411A, US5623088A, US5608111A, CN1735587A, CN1307556A, the CN1545497A etc. of Flexsys America L.P. (Flexsys America L.P.), catalysts and solvents can repeat to apply mechanically in these patents, atom utilization is high, and " three wastes " are few.The condensation reaction alkaline catalysts uses tetraalkylammonium hydroxide, particularly Tetramethylammonium hydroxide (TMAOH).Carry out hydrogenation take Tetramethylammonium hydroxide as condensation catalyst and to condensated liquid, Separation and Recovery alkali is made with extra care 4-ADPA simultaneously, and this technological process has the following disadvantages:
(1) selectivity of condensation reaction oil of mirbane and 4-ADPA yield are not high;
(2) contain alkali condensated liquid hydrogenation speed slower;
(3) hydrogenation liquid minute interval velocity is slow and emulsion arranged;
(4) rate of recovery of Tetramethylammonium hydroxide is on the low side.
Summary of the invention
The purpose of this invention is to provide a kind of Novel alkali catalyzer that overcomes Tetramethylammonium hydroxide alkaline catalysts deficiency in the above-mentioned 4-ADPA preparation process.
The contriver finds by further investigation, homemade two quaternary ammonium hydroxides cheap, Heat stability is good are mixed rear catalyzer as the reaction of oil of mirbane aniline condensation prepare 4-ADPA with Tetramethylammonium hydroxide, can overcome the deficiency that independent use Tetramethylammonium hydroxide prepares 4-ADPA.
The preparation method of a kind of 4-ADPA that the present invention proposes may further comprise the steps:
1) aniline is carried out salt-forming reaction in the presence of alkaline catalysts, generate the quaternary ammonium aniline salt, described alkali is the mixture of two quaternary ammonium hydroxides and the single quaternary ammonium hydroxide of Tetramethylammonium hydroxide, its hydroxide radical mol ratio is 99.9～0.1: 0.1～99.9, the mol ratio of control hydroxide radical and water is 1: 2～10 in the salt-forming reaction process, wherein represents the alkali number of quaternary ammonium hydroxide with hydroxide radical;
2) dropping oil of mirbane carries out condensation reaction in the saline solution to becoming, oil of mirbane and mol ratio hydroxy are 1: 0.8～2, the mol ratio of oil of mirbane and aniline is 1: 3～10, thereby acquisition contains the mixed solution of the reaction product of 4 nitrodiphenyl amine, 4-nitrosodiphenylamine and their salt;
3) the Pd/C catalyzer and add water and condensated liquid in the presence of carry out hydrogenation reaction, wherein, the mol ratio of hydroxide radical and water is 1: 5～20, described step 2) reaction product and the weight ratio of Pd/C catalyzer be 100: 0.1～1;
4) with step 3) in reaction solution carry out layering, be divided into alkali layer and oil reservoir, the oil reservoir water washs, and reclaims however, residual base wherein, oil reservoir is 100: 5～20 with the weight ratio of each water consumption, washing water and alkali are also laminated; Merge alkali lye and remove wherein organism with the toluene extraction, alkali lye is 100: 5～20 with the weight ratio of each extracting toluene, and alkali lye is used for step 1 through the concentrated cover that continues after the extraction) reaction;
5) with step 4) in oil reservoir continue hydrogenation with skeletal nickel catalyst, be aniline with wherein nitrogen benzide hydrocracking, for follow-up separation is provided convenience, oil reservoir and skeleton nickel weight ratio are 100: 0.3～1;
6) with step 5) in oil reservoir carry out rectifying separation and obtain the finished product 4-ADPA, aniline recovery continues on for step 1) reaction.
In the technique scheme:
Step 1) the hydroxide radical mol ratio of two quaternary ammonium hydroxides and Tetramethylammonium hydroxide is 99.9～0.1: 0.1～99.9 in, preferred 60～40: 40～60, and hydroxide radical and water mol ratio are 1: 2～10, preferred 1: 4～6;
Step 2) oil of mirbane and mol ratio hydroxy are 1: 0.8～2 in, preferred 1: 1.1～1.5, and oil of mirbane and aniline mol ratio are 1: 3～10, preferred 1: 4～6;
Step 3) mol ratio of hydroxide radical and water is 1: 5～20 in, preferred 1: 8～14, step 2) reaction product and the weight ratio of Pd/C catalyzer be 100: 0.1～1, preferred 100: 0.2～0.5;
Step 4) the oil reservoir washing times is 1～5 time in, preferred 2～4 times, oil reservoir is 100: 5～20 with the weight ratio of each water consumption, preferred 100: 8～12, merging alkali lye extracts 1～5 time with toluene, preferred 2～4 times, alkali lye is 100: 5～20 with the weight ratio of each toluene consumption, preferred 100: 8～12;
Step 5) oil reservoir and skeletal nickel catalyst weight ratio are 100: 0.3～1, preferred 100: 0.4～0.6.
Of the present invention pair of quaternary ammonium hydroxide structure is as follows:
This compound name is called N, N, N, N ', N ', (containing alkoxy substituted) alkylene hydroxide two ammoniums that N '-six alkyl replaces.
Wherein,
R
1And R
2The alkyl of C1～C18 independently of one another, the alkyl of preferred C1～C12, the more preferably alkyl or alkenyl of C1～C4, most preferable, ethyl, n-propyl, sec.-propyl, allyl group or butyl;
R
3, R
4, R
5And R
6The alkyl of the straight or branched of C1～C6 independently of one another, the alkyl of the straight or branched of preferred C1～C3; The more preferably straight-chain alkyl of C1～C3, most preferable, ethyl or propyl group;
R
7The alkylene of C2～C6, or the alkylene of the C2～C6 of alkoxyl group replacement; The alkylene of preferred C2～C4, or the alkylene of the C2～C4 of alkoxyl group replacement.Described alkoxyl group be methoxyl group, oxyethyl group, propoxy-, isopropoxy ,-(OCH
2CH
2)
nOH or-(OCH (CH
3) CH
2)
nOH, wherein n=1～6, preferably n=1～2.R
7Most preferably be ethylidene, propylidene, butylidene, 2-methoxyl group propylidene, 2-oxyethyl group propylidene or 2-hydroxy ethoxy propylidene.
Table 1 has been enumerated R
1And R
2Be methyl, ethyl, n-propyl, sec.-propyl, allyl group, butyl, R
3, R
4, R
5And R
6Be methyl, ethyl or propyl group, and R
7Be the two quaternary ammonium hydroxide compounds of a series of self-controls of ethylidene, propylidene, butylidene, 2-methoxyl group propylidene, 2-oxyethyl group propylidene.
Table 1 pair quaternary ammonium hydroxide compound
| Sequence number | R1、R2 | R3～R6 | R7 | The compound title |
| 1# | Methyl | Methyl | Ethylidene | Ethyl-α, β-two (trimethylammonium hydroxide) |
| 2# | Ethyl | Methyl | Ethylidene | Ethyl-α, β-two (ethyl dimethyl hydrogen ammonium oxide) |
| 3# | N-propyl | Methyl | Ethylidene | Ethyl-α, β-two (propyl-dimethyl ammonium hydroxide) |
| 4# | Sec.-propyl | Methyl | Ethylidene | Ethyl-α, β-two (sec.-propyl dimethyl hydrogen ammonium oxide) |
| 5# | Allyl group | Methyl | Ethylidene | Ethyl-α, β-two (allyl dimethyl base ammonium hydroxide) |
| 6# | Methyl | Ethyl | Ethylidene | Ethyl-α, β-two (methyl diethyl ammonium hydroxide) |
| 7# | Ethyl | Ethyl | Ethylidene | Ethyl-α, β-two (triethyl ammonium hydroxide) |
| 8# | N-propyl | Ethyl | Ethylidene | Ethyl-α, β-two (propyl group diethyl ammonium hydroxide) |
| 9# | Methyl | Methyl | Propylidene | Propyl group-alpha, gamma-two (trimethylammonium hydroxide) |
| 10# | Ethyl | Methyl | Propylidene | Propyl group-alpha, gamma-two (ethyl dimethyl hydrogen ammonium oxide) |
| 11# | N-propyl | Methyl | Propylidene | Propyl group-alpha, gamma-two (propyl-dimethyl ammonium hydroxide) |
| 12# | Sec.-propyl | Methyl | Propylidene | Propyl group-alpha, gamma-two (sec.-propyl dimethyl hydrogen ammonium oxide) |
| 13# | Allyl group | Methyl | Propylidene | Propyl group-alpha, gamma-two (allyl dimethyl base ammonium hydroxide) |
| 14# | Normal-butyl | Methyl | Propylidene | Propyl group-alpha, gamma-two (butyl dimethyl hydrogen ammonium oxide) |
| 15# | Methyl | Ethyl | Propylidene | Propyl group-alpha, gamma-two (methyl diethyl ammonium hydroxide) |
| 16# | Ethyl | Ethyl | Propylidene | Propyl group-alpha, gamma-two (triethyl ammonium hydroxide) |
| 17# | N-propyl | Ethyl | Propylidene | Propyl group-alpha, gamma-two (propyl group diethyl ammonium hydroxide) |
| 18# | Methyl | Propyl group | Propylidene | Propyl group-alpha, gamma-two (methyl dipropyl ammonium hydroxide) |
| 19# | Ethyl | Propyl group | Propylidene | Propyl group-alpha, gamma-two (ethyl dipropyl ammonium hydroxide) |
| 20# | N-propyl | Propyl group | Propylidene | Propyl group-alpha, gamma-two (tripropyl ammonium hydroxide) |
| 21# | Methyl | Methyl | Butylidene | Butyl-α, δ-two (trimethylammonium hydroxide) |
| 22# | Ethyl | Methyl | Butylidene | Butyl-α, δ-two (ethyl dimethyl hydrogen ammonium oxide) |
| 23# | N-propyl | Methyl | Butylidene | Butyl-α, δ-two (propyl-dimethyl ammonium hydroxide) |
| 24# | Sec.-propyl | Methyl | Butylidene | Butyl-α, δ-two (sec.-propyl dimethyl hydrogen ammonium oxide) |
| 25# | Allyl group | Methyl | Butylidene | Butyl-α, δ-two (allyl dimethyl base ammonium hydroxide) |
| 26# | Normal-butyl | Methyl | Butylidene | Butyl-α, δ-two (butyl dimethyl hydrogen ammonium oxide) |
| 27# | Methyl | Ethyl | Butylidene | Butyl-α, δ-two (methyl diethyl ammonium hydroxide) |
| 28# | Ethyl | Ethyl | Butylidene | Butyl-α, δ-two (triethyl ammonium hydroxide) |
| 29# | N-propyl | Ethyl | Butylidene | Butyl-α, δ-two (propyl group diethyl ammonium hydroxide) |
| 30# | Allyl group | Ethyl | Butylidene | Butyl-α, δ-two (allyl group diethyl ammonium hydroxide) |
| 31# | Methyl | Methyl | 2-methoxyl group propylidene | 'beta '-methoxy propyl group-alpha, gamma-two (trimethylammonium hydroxide) |
| 32# | Ethyl | Methyl | 2-oxyethyl group propylidene | β-ethoxycarbonyl propyl-alpha, gamma-two (ethyl dimethyl hydrogen ammonium oxide) |
| 33# | Ethyl | Methyl | 2-hydroxy ethoxy propylidene | β-hydroxy ethoxy propyl group-alpha, gamma-two (ethyl dimethyl hydrogen ammonium oxide) |
Used pair of quaternary ammonium hydroxide compound of the present invention, preferred ethyl-α, β-two (trimethylammonium hydroxide), ethyl-α, β-two (ethyl dimethyl hydrogen ammonium oxide), ethyl-α, β-two (propyl-dimethyl ammonium hydroxide), ethyl-α, β-two (methyl diethyl ammonium hydroxide), ethyl-α, β-two (triethyl ammonium hydroxide), propyl group-α, γ-two (trimethylammonium hydroxide), propyl group-α, γ-two (ethyl dimethyl hydrogen ammonium oxide), 'beta '-methoxy propyl group-α, γ-two (trimethylammonium hydroxide), β-ethoxycarbonyl propyl-α, γ-two (ethyl dimethyl hydrogen ammonium oxide), butyl-α, δ-two (trimethylammonium hydroxide), more preferably ethyl-α, β-two (trimethylammonium hydroxide), ethyl-α, β-two (ethyl dimethyl hydrogen ammonium oxide), propyl group-α, γ-two (trimethylammonium hydroxide), ethyl-α most preferably, β-two (trimethylammonium hydroxide).
In a kind of preferred embodiment, described couple of quaternary ammonium hydroxide ethyl-α, β-two (trimethylammonium hydroxide) can adopt following method preparation:
In the presence of at least a solvent that is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol and the trimethyl carbinol, ethyl-α, β-two (trimethylammonium) quaternary ammonium salt and sodium hydroxide or potassium oxide carry out ion-exchange and prepare; Wherein, ethyl-α, the mol ratio of β-two (trimethylammonium) quaternary ammonium salt and sodium hydroxide or potassium oxide is 1: 1.0～4.0, preferred 1: 1.8～2.5; Solvent load is ethyl-α, 1～15 times of β-two (trimethylammonium) quaternary ammonium salt weight, preferred 3～10 times; Temperature of reaction is 20～150 ℃, preferred 30～100 ℃; Reaction times is 1～10h, preferred 1.5～6h.
By finding with the simultaneous test of independent use Tetramethylammonium hydroxide, the use of this mixing quaternary ammonium hydroxide has following advantage:
(1) yield of the selectivity of condensation reaction oil of mirbane and 4-ADPA is high;
(2) contain the hydrogenation speed of alkali condensated liquid fast;
(3) hydrogenation liquid divides interval velocity fast and without the emulsification phenomenon;
(4) alkaline stability is good, is difficult for decomposing, and has improved the rate of recovery of alkaline catalysts, has reduced production cost.
Embodiment
Following embodiment is intended to illustrate that the mixing Quaternary Ammonium Alkali Catalyst is used for the condensation of oil of mirbane and aniline, has the advantages such as catalytic activity is high, consumption is low, and selectivity of product is high, and follow-up hydrogenation speed is fast, and the profit layering is easy, rather than limitation of the invention further.
In the following embodiments, BA represents aniline; NB represents oil of mirbane; 4-NDPA represents 4 nitrodiphenyl amine; 4-NODPA represents the 4-nitrosodiphenylamine; AZO represents nitrogen benzide; PHZ represents azophenlyene; 4-ADPA represents 4-ADPA.
Embodiment 1
Ethyl-α, the preparation of β-two (trimethylammonium hydroxide)
In the 2L four-hole bottle, add the methanol solution 383g (containing 2molNaOH) that contains 21%NaOH, begin to drip ethyl-α in 50 ℃, β-two (trimethylammonium bromide) methanol solution 976g, holding temperature is at 50～60 ℃, drip and finish, about 55 ℃, be incubated 2h.Insulation is finished, and is cooled to room temperature.Suction filtration, filter cake be with 150g * 2 methanol wash 2 times, the filter cake 257.5g that weighs, and analyzing bromide anion content is 59%.Filtrate negative pressure-0.055MPa separating methanol is to 78 ℃ of liquid temperatures, and cooling adds deionized water 400g, and band negative pressure-0.085MPa continues negative pressure piptonychia alcohol and water to 78 ℃ of liquid temperatures, the remaining liquid 475g of still, analyze ethyl-α, β-two (trimethylammonium hydroxide) content is 34.9%, bromine ion-containing 0.98%.
Embodiment 2
Ethyl-α, β-two (trimethylammonium hydroxide) generates 4-ADPA with mix the quaternary ammonium hydroxide catalysis oil of mirbane and aniline condensation and the reaction of follow-up secondary hydrogenation of Tetramethylammonium hydroxide
In the 1L four-hole bottle with stirring, thermometer, vacuum distillation device, add ethyl-α, the aqueous solution 309g that mixes quaternary ammonium hydroxide of β-two (trimethylammonium hydroxide) and Tetramethylammonium hydroxide, aniline 558g (6mol), ethyl-α wherein, β-two (trimethylammonium hydroxide) 0.24mol, Tetramethylammonium hydroxide 0.72mol, ethyl-α, β-two (trimethylammonium hydroxide) is 40: 60 with the hydroxide radical mol ratio of Tetramethylammonium hydroxide, adds up to hydroxide radical 1.2mol; Adjust absolute pressure to 40mmHg, hot water bath heating with 70～90 ℃ makes reaction system be warmed up to 60～70 ℃ of distillation dehydrations, mixes quaternary ammonium hydroxide and mixes the quaternary ammonium aniline salt with the aniline reaction generation, determine reaction end by measuring the water yield, stopped reaction when deviating from 82.2g water.System's absolute pressure is adjusted to 60mmHg, be warmed up to 70～75 ℃, slowly drip oil of mirbane 123g (1mol), constantly band water outlet in the dropping process, time for adding 4h drips and finishes 75 ℃ of insulation 2h.Deviate from material and pour the separating funnel layering into, top water layer 99.7g, bottom oil reservoir 14.5g.Oil reservoir returned add up to 808.1g in the condensated liquid.
Condensated liquid is through liquid-phase chromatographic analysis, and each component concentration is as follows: BA 57.6%, NB 0.1%, 4-NODPA 23.28%, 4-NDPA 0.84%, PHZ 0.04%, AZO 0.25%.The transformation efficiency 99.4% of NB, the selectivity 98.21% of 4-NDPA and 4-NODPA.
Above-mentioned condensated liquid 808.1g is dropped in the 2L one-stage hydrogenation autoclave, add simultaneously 263.3g water (recycle-water 181.9g in the concentrated salify of alkali and the condensation course, all the other 81.4g are deionized water) and self-control 0.8%Pd/C catalyzer 2g, use N
2And H
2Replace respectively 4 times, then pass into hydrogen, control reactor pressure is 2.0MPa, and temperature is 85 ℃, and reaction does not finish when reaction is not extremely inhaled hydrogen, and the reaction times is 0.6h; After being down to room temperature, reaction solution carries out the nitrogen press filtration, and catalyst recovery continues to apply mechanically; The filtrate standing demix, separation time is 30min, oil reservoir with 65g * 2 deionized water wash 2 times to neutral, washing water and Separation of Water laminated and after use 75g * 3 toluene extraction 3 times, water layer after the extraction is applied mechanically to condensation reaction, reclaim water layer 448g, hydroxide radical is 1.175mol, and the condensation catalyst rate of recovery counts 97.9% with hydroxide radical.Get one-stage hydrogenation oil reservoir 627.6g, extracting toluene 246g (containing BA 20.4g, 4-ADPA 0.6g).Liquid-phase chromatographic analysis content: BA 70.93%, 4-ADPA 28.68%, PHZ 0.07%, AZO0.32%.
Above-mentioned one-stage hydrogenation oil reservoir 627.6g is fed in the 1L secondary hydrogenation autoclave, adds simultaneously the 3g skeletal nickel catalyst, envelope still, displacement, control reactor pressure is 0.8MPa, and temperature is 90 ℃, and reaction does not finish when reaction is not extremely inhaled hydrogen.Get secondary hydrogenation oil reservoir 627g.Liquid-phase chromatographic analysis content: BA 71.05%, 4-ADPA 28.7%, PHZ 0.25%.
Secondary hydrogenation liquid 627g is fed into the four-hole boiling flask of 1L, the band vacuum slowly heats up to 5mmHg, remove aniline, water and front-end volatiles in the hydrogenation liquid, temperature is 220 ℃ at the bottom of still, almost during solvent-free distilling out, switch and collect main distillate fraction, rectifying is cooled to below 40 ℃ and abolishes vacuum after finishing.BA 435g, 4-ADPA 2g, PHZ 1.4g in the front-end volatiles, minute water outlet 6.5g; Main distillate fraction 177.1g, liquid-phase chromatographic analysis content: BA 0.1%, 4-ADPA 99.51%, PHZ0.23%; The residual 5.0g of still.Main distillate fraction yield 95.78%, total recovery 96.86%.
Embodiment 3～12
Each operation steps according to embodiment 2 only changes ethyl-α, and β-two (trimethylammonium hydroxide) changes from the ratio different hydroxy of Tetramethylammonium hydroxide, and its test-results is listed in table 2.
Table 2
Hydrogenation speed in the table 2 refers to, condensated liquid one-stage hydrogenation process Raw 4-NDPA and 4-NODPA complete reaction generation needed reaction times of 4-ADPA.
Claims (5)
1. the preparation method of a 4-ADPA is characterized in that, the method comprises the steps:
1) aniline is carried out salt-forming reaction in the presence of alkaline catalysts, generate the quaternary ammonium aniline salt, described alkali is the mixture of two quaternary ammonium hydroxides and the single quaternary ammonium hydroxide of Tetramethylammonium hydroxide, described pair of quaternary ammonium hydroxide is ethyl-α, β-two (trimethylammonium hydroxide), its hydroxide radical mol ratio is 99.9～0.1: 0.1～99.9, and the mol ratio of control hydroxide radical and water is 1: 2～10 in the salt-forming reaction process, wherein represents the alkali number of quaternary ammonium hydroxide with hydroxide radical;
2) dropping oil of mirbane carries out condensation reaction in the saline solution to becoming, oil of mirbane and mol ratio hydroxy are 1: 0.8～2, the mol ratio of oil of mirbane and aniline is 1: 3～10, thereby acquisition contains the mixed solution of the reaction product of 4 nitrodiphenyl amine, 4-nitrosodiphenylamine and their salt;
3) the Pd/C catalyzer and add water and condensated liquid in the presence of carry out hydrogenation reaction, wherein, the mol ratio of hydroxide radical and water is 1: 5～20, described step 2) reaction product and the weight ratio of Pd/C catalyzer be 100: 0.1～1;
4) with step 3) in reaction solution carry out layering, be divided into alkali layer and oil reservoir, the oil reservoir water washs, and reclaims however, residual base wherein, oil reservoir is 100: 5～20 with the weight ratio of each water consumption, washing water and alkali are also laminated; Merge alkali lye and remove wherein organism with the toluene extraction, alkali lye is 100: 5～20 with the weight ratio of each extracting toluene, and alkali lye is used for step 1 through the concentrated cover that continues after the extraction) reaction;
5) with step 4) in oil reservoir continue hydrogenation with skeletal nickel catalyst, be aniline with wherein nitrogen benzide hydrocracking, for follow-up separation is provided convenience, oil reservoir and skeleton nickel weight ratio are 100: 0.3～1;
6) with step 5) in oil reservoir carry out rectifying separation and obtain the finished product 4-ADPA, aniline recovery continues on for step 1) reaction.
2. the preparation method of 4-ADPA according to claim 1 is characterized in that, described step 1) in the hydroxide radical mol ratio of two quaternary ammonium hydroxides and Tetramethylammonium hydroxide be 60～40: 40～60, hydroxide radical and water mol ratio are 1: 4～6.
3. the preparation method of 4-ADPA according to claim 1 is characterized in that, described step 2) oil of mirbane and mol ratio hydroxy be 1: 1.1～1.5, oil of mirbane and aniline mol ratio are 1: 4～6.
4. the preparation method of 4-ADPA according to claim 1 is characterized in that, described step 3) in the mol ratio of hydroxide radical and water be 1: 8～14, step 2) reaction product and the weight ratio of Pd/C catalyzer be 100: 0.2～0.5.
5. the preparation method of 4-ADPA according to claim 1 is characterized in that, described step 5) oil reservoir and skeletal nickel catalyst weight ratio be 100: 0.4～0.6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010112231 CN101830811B (en) | 2010-02-23 | 2010-02-23 | Preparation method of 4-aminodiphenylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010112231 CN101830811B (en) | 2010-02-23 | 2010-02-23 | Preparation method of 4-aminodiphenylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101830811A CN101830811A (en) | 2010-09-15 |
| CN101830811B true CN101830811B (en) | 2013-04-03 |
Family
ID=42715054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010112231 Active CN101830811B (en) | 2010-02-23 | 2010-02-23 | Preparation method of 4-aminodiphenylamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101830811B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012208325A (en) * | 2011-03-30 | 2012-10-25 | Tosoh Corp | Quaternary ammonium compound, method of manufacturing the same, and developer composition containing the same |
| CN108623475A (en) * | 2017-03-20 | 2018-10-09 | 中国石油化工股份有限公司 | A kind of method that quaternary ammonium alkali collection puts recycling in order |
| CN107118108B (en) * | 2017-06-06 | 2018-07-20 | 青岛科技大学 | A kind of catalytic hydrogenation method of aniline-nitrobenzene condensation liquid |
| CN112439454B (en) * | 2019-09-05 | 2023-04-07 | 中国石油化工股份有限公司 | RT base condensation catalyst and preparation method thereof |
| CN110668956B (en) * | 2019-10-22 | 2021-03-23 | 山东尚舜化工有限公司 | Method for desalting and purifying water phase through water washing extraction in RT base production process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5117063A (en) * | 1991-06-21 | 1992-05-26 | Monsanto Company | Method of preparing 4-aminodiphenylamine |
| CN1545497A (en) * | 2001-07-23 | 2004-11-10 | Process for preparing 4-aminodiphenylamine | |
| CN101717339A (en) * | 2009-12-08 | 2010-06-02 | 江苏扬农化工集团有限公司 | Double quaternary ammonium base compound and preparation method as well as application thereof |
-
2010
- 2010-02-23 CN CN 201010112231 patent/CN101830811B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5117063A (en) * | 1991-06-21 | 1992-05-26 | Monsanto Company | Method of preparing 4-aminodiphenylamine |
| CN1545497A (en) * | 2001-07-23 | 2004-11-10 | Process for preparing 4-aminodiphenylamine | |
| CN101717339A (en) * | 2009-12-08 | 2010-06-02 | 江苏扬农化工集团有限公司 | Double quaternary ammonium base compound and preparation method as well as application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101830811A (en) | 2010-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101830811B (en) | Preparation method of 4-aminodiphenylamine | |
| CN100400622C (en) | Method of preparing biological diesel oil using solid base catalyst | |
| CN104370722A (en) | Butanone preparation and refining method | |
| CN107915644B (en) | A method of p-aminophenyl ether is prepared by raw material of paranitrochlorobenzene | |
| CN104478676B (en) | Preparation and the refining system of butanone | |
| CN105085282B (en) | Preparation method for alkyl alcohol amine | |
| CN102432430A (en) | Method for preparing trimethylolpropane through multistage circulating hydrogenation | |
| CN103357357A (en) | Jet type membrane reactor and method for preparing methylaniline by continuous catalytic hydrogenation | |
| CN101891631B (en) | Method for preparing pendimethalin | |
| CN102372639A (en) | Method for preparing 4-aminodiphenyamine | |
| CN102504891A (en) | Preparation method of glyceryl biofuel additive | |
| CN113024385B (en) | Preparation method of 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl | |
| CN103497157B (en) | 2-imidazolidone synthesis method | |
| CN102807500A (en) | Method for liquid-phase preparation of N, N-dimethylacetamide | |
| CN103193660B (en) | Synthetic method of 4-alkoxy phenylamine compound | |
| CN101747156A (en) | New method for preparing 2,4-ditert-pentyl-phenol | |
| CN109096058B (en) | Ring-opening reaction device for epoxyalkane | |
| CN102876466A (en) | Method for catalyzing ester exchange reaction with alkaline ionic liquid | |
| CN103664616A (en) | Method and device for producing benzyl benzoate | |
| CN107417541A (en) | The preparation technology of para aminophenyl ethyl ether and aniline | |
| CN102010296A (en) | Method for preparing cyclopentanol from cyclopentene through hydration | |
| CN107540522A (en) | A kind of production technology of sec-butyl alcohol | |
| CN101205174B (en) | Method for preparing p-alkoxy phenol | |
| CN215209192U (en) | Sec-butyl alcohol production device | |
| CN101875723B (en) | Resin and preparation method thereof, and catalyst used for preparing biodiesel and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |